Glyceryl Ether Compounds and their Use

ABSTRACT

Glyceryl ether compounds prepared by the reaction of glycerol and olefin epoxides are disclosed. The compounds are renewable biomass-based surfactants useful as detergents and emulsifiers in formulations for cleaning, laundry, personal care, cosmetics, and industrial uses.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 60/738,987, entitled “Glyceryl ether compounds and theiruse,” filed on Nov. 22, 2005, which is incorporated by reference in itsentirety herein.

TECHNICAL FIELD

The present disclosure relates to the preparation of compounds fromglycerol and olefin epoxides.

BACKGROUND

Many surfactant compounds and soaps with various properties are known inthe art. Of particular interest are non-ionic and ionic surfactantcompounds that perform well in hard water containing elevated levels ofalkali-earth metal salts. However, such surfactants are typicallymanufactured entirely, or in major part, from various expensive andoften highly hazardous petrochemicals via complex chemical methods.Therefore, well-performing surfactants that utilize abundant, renewable,and inexpensive raw materials and simpler chemical synthesis methods arehighly desired.

SUMMARY

Provided herein are a series of glyceryl ether compounds that have beenfound to be surfactant compounds having good solubilizing andemulsifying properties, including performance in water containing highconcentrations of calcium and magnesium ions.

Glyceryl ether compounds can be prepared through the reaction ofepoxidized normal alpha-olefin (NAO) compounds of formula (2), whereinR³ can be a C₆-C₃₀ linear alkyl, or preferably, a

C₆-C₁₄ linear alkyl, and glycerol, or a protected glycerol of formula(3):

wherein R⁴ and R⁵ are independently selected from the group consistingof hydrogen; linear, branched, or cyclic alkyl; linear, branched, orcyclic alkenyl; aryl; and arylalkyl. The reaction can be performed inthe presence of an acid or base catalyst. In certain embodiments, thereaction can be followed by deprotection of the ketal or acetalprotecting group on the glyceryl moiety.

Examples of compounds prepared from glycerol, or a protected glycerol,and an epoxidized NAO can include the following formula:

wherein one of R¹ and R² is hydrogen and the other is a C₆-C₃₀ linearalkyl; and X is selected from the group consisting of:

wherein R⁴ and R⁵ are as defined above.

In another embodiment, glyceryl ether compounds can be prepared from thereaction of glycerol, or a protected glycerol of formula (3), and anepoxidized triglyceride, or an epoxidized unsaturated fatty acid ester,wherein the fatty acid fragment has from 8 to 24 carbon atoms, and thealcohol fragment is a C₁-C₁₂ linear or branched monohydric alcohol. Asabove, the reaction can be performed in the presence of an acid or basecatalyst. In certain embodiments, the reaction can be followed bydeprotection of the ketal or acetal protecting group on the glycerylmoiety. In addition, the ester moiety can be converted to a freecarboxyl group, a carboxylic salt, or an amide.

Examples of such compounds can include the formula:

wherein one of A or B is hydrogen and the other is selected from thegroup consisting of carboxyl, carboxylate salt, and ester; m and n areindependently integers from 0 to 20, and the value of the sum of m+n isin the range from 8 to 21; and Y and Z are independently selected fromthe group consisting of

The reaction product can also include the formula:

wherein R⁶ is selected from hydrogen or a C₁-C₁₀ linear or branchedalkyl; W is selected from the group consisting of:

and V is selected from the group consisting of:

In some embodiments, the compounds above can be converted into theircorresponding salt. In addition, the ester moiety in the above compoundscan be converted to a free carboxyl group, a carboxylic salt, or anamide.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features,objects, and advantages of the invention will be apparent from thedescription and drawings, and from the claims.

DETAILED DESCRIPTION

Provided herein are a series of glyceryl ether compounds that have beenfound to be surfactant compounds with good solubilizing and emulsifyingproperties, including performance in water containing a highconcentration of calcium and magnesium ions. Glyceryl ether compoundsare produced from glycerol, which is an abundant and inexpensiverenewable material available as a by-product of the production ofbiodiesel fuels from triglycerides, and from relatively inexpensiveepoxides of unsaturated compounds such normal alpha-olefins (NAO), orfrom epoxidized unsaturated fatty acid esters.

The first objective of the present disclosure is the provision ofhydroxy alkyloxy-glyceryl ethers of formula (1):

wherein one of R¹ or R² is hydrogen and the other is a C₆-C₃₀ linearalkyl, or preferably, a C₆-C₁₄ linear alkyl.

The compounds of formula (1) can be prepared from the 1,2-epoxides ofNAO having formula (2):

wherein R³ is a C₆-C₃₀ linear alkyl, and preferably, a C₆-C₁₄ linearalkyl.

The compounds of formula (2) are reacted with either glycerol or,preferably, with a protected form of glycerol, in the presence of asuitable catalyst. The protected form of glycerol can be a ketal oracetal of the glycerol of the formula (3):

wherein R⁴ and R⁵ are each independently selected from hydrogen; linear,branched, or cyclic alkyl; linear, branched, or cyclic alkenyl; aryl; oraralkyl. Preferably, R⁴ and R⁵ are not both hydrogen.

Many ketals and acetals of formula (3), and methods for theirpreparation from glycerol, are known in the art. Typically, dioxolanesof formula (3) are prepared by reacting glycerol with a suitable linear,branched, or cyclic ketone or aldehyde in the presence of an acidcatalyst, and under conditions allowing for removal of the water formedin the reaction. The removal of water is typically accomplished by adistillation if the boiling point of the ketone and aldehyde are bothsufficiently above the boiling point of water, or by an azeotropicdistillation with a suitable co-solvent. Dioxolanes of formula (3) canalso be prepared by trans-ketalization or trans-acetalization of ketalsor acetals of formula (4) with glycerol:

wherein R⁶ and R⁷ are independently selected from a C₁-C₆ linear orbranched alkyl.

Suitable glyceryl ketals and acetals are compounds typically formed fromglycerol and simple and inexpensive ketones and aldehydes that arereadily available at industrial scale. Non-limiting examples of suchketones and aldehydes include acetone, 2-butanone, methyl isobutylketone, alkyl isopropyl ketones, cyclohexanone, cyclopentanone,isophorone, cycloheptanone, cyclododecanone, dihydroisophorone,menthone, camphor, and linear or branched aliphatic aldehydes,preferably, having 6 or more carbon atoms.

Acetals of glycerol and linear or branched aliphatic aldehydes commonlyexist as an equilibrating mixture of 1,2-acetals(4-hydroxymethyl-1,3-dioxolanes) and 1,3-acetals(4-hydroxymethyl-1,3-dioxanes). Even in such mixtures, they are suitablefor reaction with epoxides, but it is understood that 1,3-acetals of2-glyceryl ether adducts may be formed. The presence of varyingquantities of 1,3-acetals (or 1,3-ketals) in the starting materials doesresult in the formation of varying quantities of 1,3-ketals of2-glyceryl ether products. This may diminish the usefulness of theresulting mixtures of compounds in the preparation of surface-activesubstances. It is preferred, therefore, that epoxides be reacted with1,2-ketals of glycerol. In addition, acetals are more prone to theformation of peroxides and often have undesirable or annoying odors oftrace free aldehydes.

When glyceryl ketals and acetals of formula (3) are reacted with anepoxide of formula (2), the resulting product is a mixture ofstereoisomers having formula (5):

wherein one of R¹ or R² is hydrogen and the other is a C₆-C₃₀ linearalkyl, or preferably, a C₆-C₁₄ linear alkyl; and R⁴ and R⁵ are eachindependently selected from hydrogen; linear, branched, or cyclic alkyl;linear, branched, or cyclic alkenyl; aryl; or aralkyl.

The compound of formula (5) can be converted to the desired triol offormula (1), by treatment with sufficient amount of water or alkanol inthe presence of an acid catalyst that is sufficient to cause hydrolysisor trans-ketalization but not elimination reactions. The deprotectionstep requires very mild conditions and may be expedited by heating thereaction mixture to the reflux temperature of the water or alkanol. Whenwater is used, the ketone or aldehyde of formula R⁴—(C═O)—R⁵ isreleased, and can be separated and re-used in the process of making theprotected glycerol of formula (3). When an alkanol is used, the ketal oracetal of formula (4) is released, which also can be separated andre-used in the synthesis of the compound of formula (3). The alkanolused in this reactions is preferably a linear or branched primary orsecondary alkanol having from 1 to 6 carbon atoms.

The reaction between NAO epoxide of formula (2) and glycerol, or aglycerol derivative of formula (3), is typically carried out in thepresence of a suitable catalyst. Catalysts for reacting epoxides offormula (2) with glycerol or with a compound of formula (3) can includevarious acids, and other catalysts known in the art. Such conditions arealso generally applicable to the reactions of glycerol, or the compoundof formula (3), with an epoxidized unsaturated fatty acid ester.Non-limiting examples of such catalysts include strong mineral acids,such as sulfuric, hydrochloric, hydrofluoroboric, hydrobromic acids,p-toluenesulfonic acid, camphorosulfonic acid, methanesulfonic acid, andthe like. Various resins that contain protonated sulfonic acid groupsare also useful as they can be easily recovered after completion of thereaction. Examples of suitable acids further include Lewis acids, forexample, boron trifluoride and various complexes of BF₃, exemplified byBF₃ diethyl etherate. Other non-limiting examples of useful Lewis acidsinclude halides of tin, titanium, aluminum, iron, silica, acidicalumina, titania, zirconia, various acidic clays, and mixed aluminum ormagnesium oxides. Activated carbon derivatives comprising mineral,sulfonic, or Lewis acid derivatives can also be used.

The reaction can also be performed with a base catalyst. Various basessuch as alkali metal alkoxides or hydroxides can be used as catalysts inthe reaction between compound (2) and glycerol or compound (3). Usefulsolid catalysts are described in the United States Patent ApplicationNo. 2004/0077904 (Nagasawa, Atsushi, et al.; Apr. 22, 2004), andreferences cited therein.

The present disclosure is not limited to a specific catalyst or anamount of catalyst. One of ordinary skill in the art can practice manyvariations on the part of the catalyst composition and the amounts used.Elevated temperatures may be used to accelerate the reaction with lessreactive catalysts, however, the temperature of the reaction mixture isnot critical for succeeding in making a quantity of the glyceryl etherproduct, as even with less active catalysts the reaction still proceedsto yield the desired compounds. The amount and type of catalyst dependson the specific chemical composition of the epoxide and glycerol orglycerol derivative of formula (3), used in a reaction and can bereadily established by one skilled in the art. It is understood that theuse of different catalysts, such as different acids or bases, can anddoes result in the formation of the products of formula (1) or (5) withvarying stereocompositon, because nucleophilic opening of epoxides inthe presence of acids or in the presence of bases proceeds withdifferent regioselectivity and stereoselectivity.

The reaction can be carried out in the presence of an optionalco-solvent that is substantially inert under the reaction conditions andis often removed at the end of the reaction by distillation. Typically,it is desired to use a sufficient quantity of a co-solvent to minimizecross-linking of the epoxides via ether bond formation. Non-limitingexamples of suitable co-solvents include saturated hydrocarbons, ethers,and polyethers. Any excess solvent remaining after completion of thereaction can be removed by distillation at normal or reduced pressure.

It has been found that compounds of formula (3) are very good solventsfor NAO epoxides. The reaction between an epoxide and the glycerolderivative of formula (3) can also be conveniently performed in anexcess of the latter compound, typically 2 to 20 times molar excess.When insufficient excess of the compound (3) is used, however,oligomeric adducts of compound (3) and two or more glycol etherfragments are formed as the major products. These compounds are alsouseful as surfactants, however, they are more expensive to manufacturedue to the cost of the epoxide involved.

When free glycerol is reacted with NAO epoxides of formula (2), thesereactants are generally immiscible in the absence of a suitableco-solvent. In such an embodiment, the reaction can be facilitated byvigorous stirring and by addition of one or more phase transfercatalysts, including surfactants of formula (1) or othersurfactants/emulsifiers. Ether compounds that are alkylated oligomers ofethylene oxide are also useful as co-solvents and phase transferreagents for this reaction. Reaction of unprotected glycerol with NAOepoxides of formula (2) typically results in the formation of higherquantities of various byproducts, due to epoxide oligomerization and dueto epoxide opening reactions that involve more than one hydroxyl groupof the same glycerol molecule.

The compounds of formula (1) can be obtained and used in a neat(solventless) form, or as a concentrated solution in an aqueous solvent,including pure water and water-solvent mixtures.

Neat compositions of formula (1) are most conveniently obtained bydeprotecting a compound of formula (5) in the presence of excess alkanolas described above, followed by removal of the alkanol and compound (4)by distillation. It is also advantageous to remove any other volatileodoriferous impurities that may be present in the industrial grade NAOepoxides (such as traces of hydrocarbons, alkanals and alkanones).

The compounds of formula (1) in neat form, when obtained from NAOepoxides having from 8 to 16 carbon atoms, are paste-like solids orviscous liquids, while compounds from NAO epoxides having 18 or morecarbon atoms are waxy solids. The compounds from NAO epoxides havingfrom 8 to 18 carbon atoms have very good solubility in water,water-alcohol, and water-propylene glycol mixtures, givingcharacteristic opalescent smectic appearance to such solutions. Thecompounds from NAO epoxides having 18 carbon atoms or more, on the otherhand, are somewhat less soluble and may precipitate in cold water. Goodsolubility properties are advantageous for using compounds of formula(1) in various formulations where surfactant or emulsifying propertiesare desired. The compounds of formula (1) are stable in cold and hotaqueous solutions over a broad range of pH values (i.e, from pH 2 to pH13). Compounds of formula (1) are non-ionic surfactants, and theirsurfactant and emulsifying or micelle-forming properties are notsubstantially affected by the presence of alkali-earth metal ions in thesolution.

Compounds of formula (1) can be used in a manner substantially similarto that of other non-ionic surfactants known in the art. Compounds offormula (1) can thus be used alone or in various combinations with othersurfactants, solvents, glycols and polyols, fragrances, colors,biologically-active and inert additives, enzymes, inorganic salts suchas chloride and sulfate salts of alkali metals, fabric wetting agents,antiseptics, and bleaching agents. The compounds can used in cleaning,dishwashing, laundry, cosmetic and personal care products, degreasingpreparations, and the like. Effective concentrations for use ofcompounds of formula (1) depend on the intended use of the formulationand can be easily established empirically by one of ordinary skills inthe art. The effective concentrations for compounds of formula (1) cantypically range from 0.001% to 100% of the formulated product.

In another embodiment, surfactant compounds can be prepared fromepoxides of unsaturated fatty acid esters. These compounds are preparedin the manner similar to the above-described methods for makingcompounds of formula (1) from the NAO epoxides of formula (2).

The following terms apply:

Unsaturated fatty acids mean linear monocarboxylic acids having from 10to 24 carbon atoms and at least one double bond. The double bonds can bein any positions, conjugated with each other or non-conjugated, but notin allenic arrangements, and any of the double bonds can beindependently cis or trans. Preferably, fatty acids have one or twodouble bonds, and more preferably, only one double bond.

Esters of fatty acids mean esters of the above-described fatty acidswith monohydric alcohols.

Monohydric alcohols are linear or branched primary or secondary alkanolshaving from 1 to 12 carbon atoms. Preferred examples of alkanols aremethanol, ethanol, propanol, isopropanol, butanol, secondary butanol,isobutanol, isoamyl alcohol, and 2-ethylhexanol.

It is understood that in industrial practice, where mixed fatty acidcompositions are used, not all of the fatty acid esters present in thestarting material can be unsaturated and some fully saturated fatty acidgroups can be present in the ester mixtures. In fact, it iscost-advantageous to use mixtures of unsaturated and saturated fattyacid esters such as triglycerides of typical vegetable oils (e.g.,soybean oil, linseed oil, canola oil, safflower oil, sunflower oil, cornoil, castor oil, their blends and the like). It is preferred, however,that the mixed fatty acid esters contain predominantly unsaturated fattyacid esters. It is also preferred that a fatty acid ester with a highcontent of mono-unsaturated fatty acid ester is used, such as thecompositions found in high oleic canola oil. Esters of 10-undecylenicacid are also preferred. Another preferred starting material is amixture of methyl esters of fatty acids derived by trans-esterificationof vegetable oils (e.g. of soybean oil, canola oil and other unsaturatedtriglycerides commonly used in the industrial production of biodieselfuel).

Various unsaturated fatty acid esters can be optionally blended, mixed,partially hydrogenated, or otherwise isomerized to change the positionor stereochemistry of the double bonds. It is particularly advantageousto isomerize natural mono-unsaturated fatty acid esters with the purposeof shifting the position of the double bond to a position in proximityof the carboxyl group, e.g., the 2,3-position to yield alk-2-enoicesters. Similarly, it is preferred that natural di-unsaturated fattyacid esters be isomerized to alka-2,4-dienoic esters. Such isomerizationproducts are favored during catalytic isomerization of esters in thepresence of an acid or a Lewis acid, or in the presence of a metalcatalyst. Metal catalysts ordinarily used in the hydrogenation ofalkenes can include palladium, ruthenium, iridium, copper chromite,nickel salts, and the like.

Epoxidized unsaturated fatty acid ester means that at least one of thedouble bonds of the unsaturated fatty acid ester is oxidized to an epoxygroup. Such oxidations are well known in the art and can be readilyaccomplished at an industrial scale, e.g., by using hydrogen peroxideand a carboxylic acid (e.g. formate or acetate), or by the halohydrinmethod. It is preferred, however, that epoxidation of at least one ofthe double bonds present in the unsaturated fatty acid ester isaccomplished. It is understood that in practice, epoxidized fatty acidesters may contain various quantities of by-products arising fromhydrolysis or rearrangement of epoxides and from cross-linking of thefatty acid chains. Use of epoxidized fatty acid esters containing smallquantities of epoxidation by-products and epoxide decompositionby-products is fully within the scope of the present disclosure.

Glyceryl ethers derived from epoxides of mono-unsaturated fatty acidesters can have the formula (6):

wherein one of A or B is hydrogen and the other is selected from thegroup consisting of carboxyl, carboxylate salt, and ester; and n and mare integers each having values from 0 to 20, and the value of the sumof m+n is in the range from 8 to 21.

When bis-epoxides or tris-epoxides of unsaturated fatty acid estershaving epoxy groups positioned in close proximity to one another areused, an intra-molecular epoxide opening reaction can take place,resulting in the formation of one or more ether bonds connecting twocarbon atoms of the continuous fatty acid carbon chain. Typically, suchether bonds result in the formation of a tetrahydrofuran (major) andtetrahydropyran (minor) rings. Complex mixtures of stereoisomers ofoxygenated derivatives of fatty acid esters are formed. For example,representative isomers of the such surfactant products from abis-epoxide from a di-unsaturated fatty acid having two double bondsseparated by a methylene group can have formulae (7a) and (7b):

wherein A, B, m, and n are as defined above.

Compounds of formula (7a) and (7b) are typically formed as mixtures thatcan also include other adducts, such as di(glyceryl)ether adductsresulting from the opening of each of the epoxy groups with a differentglycerol fragment, thereby resulting in oxygenated fatty acidderivatives comprising two hydroxyl groups and two pendant glycerylether groups.

Preferably, the glyceryl ether adducts of epoxidized fatty acid estersare formed by the reaction of a protected glycerol of formula (3),followed by the removal of any excess compound of formula (3) bydistillation, and by deprotection of the glyceryl ether ketal/acetalmoiety.

Alternatively, the glyceryl ether adducts of epoxidized fatty acidesters can be prepared by treating epoxidized triglycerides with thecompound of formula (3) in the presence of catalyst substantiallysimilar to the catalysts described. In such an embodiment, triglyceridepolyol compounds are formed. These compounds have free secondaryhydroxyl groups and glyceryl ether pendant groups attached to the fattyacid chains. Optionally, ether bonds may also be present in such adductsand the ether bonds can connect two carbon atoms of one fatty acid chain(thereby forming a tetrahydrofuran or a terahydropyran ring) or twodifferent fatty acid chains.

Such adducts of glycerol or of a ketal/acetal protected glycerol with anepoxidized triglycerides are typically prepared from epoxidized soybeanoil, linseed oil and the like. These adducts have been found to beuseful in the production of compounds of formula (6), (7a), and (7b), aswell as their corresponding ketals/acetals of formulae (8), (9a) and(9b):

The conversion of the triglyceride adducts to the compounds (8), (9a)and (9b) is most readily accomplished by a trans-esterification reactionwith a monohydric alkanol in the presence of catalytic amount of base.Non-limiting examples of suitable bases are hydroxides of alkali oralkali-earth metals or alkoxides of alkali metals and alkanols.Deprotection of ketal/acetal groups of the compounds (8), (9a), and (9b)is readily accomplished by using an alkanol in the presence of an acidcatalyst, thereby resulting in the formation of the compounds (6), (7a),and (7b), respectively.

The deprotection of the ketal groups and trans-esterification oftriglyceride ester bonds with a monohydric alcohol can also be combinedand carried out in the presence of a catalytic amount of an alkanol andan acid. Typically, an excess of monohydric alkanol is used, and whenthe reaction is substantially complete, excess alkanol and ketal (4) areremoved by distillation. Any glycerol formed in this reaction can alsobe separated and re-used in the synthesis of glyceryl ether compounds asdescribed herein.

The resulting ether adducts of glycerol and the hydroxylated fatty acidesters (as exemplified by compounds of formula (6), (7a), (7b)) areuseful non-ionic surfactants that can be used in various formulations ina manner substantially similar to the non-ionic surfactants of formula(1) disclosed above.

The carboxyl group in the ether adducts of glycerol and the hydroxylatedfatty acid esters can optionally be saponified to furnish a salt(typically, alkali, alkali-earth, ammonium, or an amine salt). Thecarboxyl group can also be protonated. Furthermore, the carboxyl groupcan be amidated with a primary or a secondary alkylamine or anaminoalcohol. Such secondary derivatives resulting from the chemicalmodifications at the carboxyl group are useful ionic surfactants thatwork well in hard water. Similarly to compounds of formula (1), (6),(7a), and (7b), these compounds can be used to formulate varioussurfactant and emulsifier preparations according to methods known in theart.

EXAMPLES Example 1

5 g of decene-1,2-oxide of 94% purity was dissolved in 15 ml of solketaland stirred by means of magnetic stirring at room temperature (25° C.).Boron trifluoride diethyl etherate (0.05 ml) was added by means of asyringe, and the reaction mixture was stirred for 20 min. During thistime, an exothermic reaction was observed and the temperature wasallowed to rise to about 55° C. 0.5 g of ammonium fluoride was added andthe suspension was stirred for another 2 hrs. The resulting mixture wasfiltered, and unreacted solketal was removed under reduced pressure. Theresulting colorless liquid (7.8 g) was analyzed by gaschromatography-mass spectrometry (GC-MS) and was found to containapproximately 85% of a mixture of stereoisomers of ketal compounds offormulae (10a) and (10b):

These compounds were detected as a mixture that manifested as threepartially resolved peaks on the GC chromatogram.

Small amounts of the stereoisomers of the compound of formula (10c) werealso present in the isolated reaction mixture:

The isomers of compound (10a) and (10b) had representative mass-spectrashown below.

Partial TIC chromatogram of the elution area where isomeric compounds(10a) and (10b) elute:

Representative mass-spectra of the peaks of the above chromatogram:

Example 2

The reaction was carried out according to Example 1, except 5 g ofoctadecene-1,2-oxide of 85% purity was used, and the reaction wascarried out at 60° C. to facilitate dissolution of the starting materialin solketal. The resulting waxy and oily Mixture of compounds (5.7 g)was analyzed by GC-MS and was found to contain approximately 75% ofmixed isomeric compounds having formula (11a) and (11b):

Partial TIC chromatogram of the elution area where isomeric compounds(11a) and (11b) elute:

Representative mass-spectra of peaks of the above chromatogram:

Example 3

1 g of reaction product obtained in Example 1, 5 g of water, and 0.01 gof sulfuric acid were combined by means of continuous magnetic stirringand heated for 2 hours at 90-95° C. The reaction mixture was then cooledto room temperature, neutralized by means of addition of calciumcarbonate (0.1 g), and filtered. The reaction mixture was acharacteristic opalescent smectic solution. Upon evaporation of waterunder reduced pressure, 0.6 g of viscous oily-waxy opalescent residuewith a pearl-like appearance was obtained. The resulting compoundcontained predominantly stereoisomers of compounds 12a and 12b:

The aqueous solutions of the mixture of isomers of compounds (12a) and(12b) were able to form stable emulsions of hexane in water at (1:1 vol)when the concentrations of compounds (12a) and (12b) were in excess of0.2%. The emulsifying properties of compounds (12a) and (12b) were notdisrupted by the addition of 0.2% calcium chloride or magnesiumchloride.

Examples 4-5

1 g of the reaction product obtained in Example 1, 5 g of methanol(Example 4) or n-butanol (Example 5) and 0.05 g of p-toluene sulfonicacid were dissolved and stirred by means of magnetic stirring for 48hours at room temperature. The resulting solution was neutralized by theaddition of 0.1 g of calcium carbonate, stirred for 1 hour and filtered.The excess alcohol and small quantities of 2,2-dimethoxypropane (Example4) or 2,2-dibutoxypropane (Example 5) were removed under reducedpressure, affording 0.55 and 0.58 g, respectively, of a materialcontaining compounds of formula (12a) and (12b); identical in allrespects to the compounds prepared in Example 3.

Example 6

The reaction was carried out according to Example 3, except that thestarting material prepared in Example 2 was used. The resulting waxysolid (3.9 g, m.p. 42-46° C.) contained predominantly compounds offormula (13a) and (13b):

Aqueous solutions of the mixture of isomers of compounds (13a) and (13b)were able to support stability of emulsions of water in hexane. Theemulsifying properties of compounds (13a) and (13b) were notsubstantially disrupted by the addition of 0.2% calcium chloride ormagnesium chloride.

Examples 7-8

The synthesis was carried out according to Examples 4-5, except thestarting material used was prepared according to Example 2. The isolatedmixture of compounds (13a) and (13b) was in all respects identical tothat obtained in Example 6.

Example 9

10 g of decene-1,2-oxide and 25 ml of glycerol were vigorously stirredat room temperature. Boron trifluoride diethyl etherate was added bymeans of a syringe in 10 minute intervals (3 portions of 0.2 ml each),and the reaction mixture was stirred for an additional hour. Theresulting mixture was then left standing and excess glycerol wasseparated by means of a reparatory funnel. The upper phase liquidcontained a mixture of adducts comprising compounds of formula (11a),(11b), (11c), and the isomers of a bis-hydroxydecyl glyceryl ether. Theresulting mixture had a similar surfactant and emulsifying capability tothe material prepared in Example 2.

Example 10

The reaction was carried out according to the conditions of Example 1,except the starting material was a fully epoxidized mixture of fattyacid methyl esters obtained by methanolic trans-esterification ofepoxidized soybean oil (Vicoflex® brand, Arkema), and the reaction withsolketal was carried out at 60° C. The resulting mixture of products(6.4 g) was analyzed by GC-MS and was found to contain severalstereoisomers of solketal ether adducts among which were compounds offormulae (14a), (14b), (15a), (15b), (15c), and (15d), whereinR⁶=methyl:

Methyl esters of hexadecanoic acid and octadecanoic acid were alsopresent. Small quantities of other unidentified modified fatty acidester products, as well as products arising from the rearrangement ofthe epoxides on the carbonyls, were also observed.

Example 11

3 g of the material obtained in Example 10 was heated to 100° C. at 0.5mm vacuum for 24 hours with stirring to reduce the content of methylester of hexadecanoic acid to a value less than approximately 1% byweight of the starting material (approximately 10% weight loss). Theresulting oil was dissolved in 20 ml of methanol and refluxed with 0.2 gof tosic acid for 24 hours. The reaction mixture was then neutralizedwith 0.5 g of calcium carbonate, filtered, and the methanol and2,2-dimethoxypropane were removed under reduced pressure to give 1.9 gof a waxy low-melting solid comprising a mixture of glyceryl etheradducts of methyl esters of modified fatty acids represented by formulae(16a), (16b), (17a), (17b), (17c), (17d):

wherein R⁶ is methyl.

The waxy product was then saponified in 20 ml of water at 60° C., bystirring and titrating dropwise with 1 N aqueous sodium hydroxide tomaintain pH 8-10. The resulting soapy solution contained sodium salts ofcarboxylic acid compounds of formulae (18a), (18b), (19a), (19b), (19c),and (19d):

The mixture of sodium salts had good surfactant and emulsifyingproperties that were not adversely affected in the presence of 0.1%calcium chloride.

Example 12

5 g of epoxidized soybean oil (Vicoflex® 7170 brand, Arkema) wasdissolved in 20 ml of solketal. The reaction mixture was heated andstirred at 60° C., and 0.2 g of BF₃ diethyl etherate was added over 15min (4 portions of 0.05 ml each). The reaction mixture was stirred for 1hour and then cooled to the room temperature. The catalyst wasneutralized by stirring with 0.5 g of ammonium fluoride for 1 hour andthe whole was filtered. Excess solketal was removed by distillationunder reduced pressure to give 5.7 g of a transparent, free flowing,practically colorless, very viscous liquid that comprised a mixed etherpolyol adduct of epoxidized fatty acid triglyceride and1,2-isopropylidene glycerol.

1 g of the resulting material was dissolved in 10 g of methanol andrefluxed for 24 hours in the presence of 0.05 g of p-toluenesulfonicacid. The solution was then neutralized by the addition of 0.2 g ofcalcium carbonate, stirred for 2 hrs and filtered. Methanol was removedunder reduced pressure and about 0.8 g of a waxy solid was obtained. Thewaxy solid was dissolved in 10 ml of water and saponified in a mannerdescribed in Example 11. The resulting soapy solution contained sodiumsalts of a mixture of compounds that had a very similar composition andsurfactant properties to the material obtained in Example 11.

Example 13

The synthesis was carried out as in Example 1, except that 25 g of1,2-glyceryl ketal of menthone was used in place of solketal, and thereaction was carried out at 60° C. After removal of any excess1,2-glyceryl ketal of menthone, the resulting oil was treated bystirring with methanol (40 ml) in the presence of 0.2 g of p-toluenesulfonic acid at room temperature for 4 days. The reaction wasneutralized by stirring with 2 g of calcium carbonate for 24 hours andthen filtered. The filtrate was evaporated under reduced pressure todistill out any methanol, menthone dimethyl ketal, and menthone present.The surfactant properties of the resulting mixture of products weresubstantially similar to those obtained in Example 3.

Example 14

The synthesis was carried out as in Example 13, except that 1,2-glycerylketal of camphor was used.

Examples 15-17

The synthesis was carried out according to Example 1, except that inplace of decene-1,2-oxide, 5 g of one of the following epoxides was used(each was 90-94% pure):

(Example 15) dodecene-1,2-oxide,

(Example 16) tetradecene-1,2-oxide,

(Example 17) hexadecane-1,2-oxide.

The resulting product mixtures were deprotected on the part of removalof the acetonide groups according to the conditions of Example 3. Theresulting hydroxyalkyl glyceryl ether adduct mixtures were similar intheir surfactant and emulsion properties to those obtained in Example 3.

A number of embodiments of the disclosure have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the disclosure.Accordingly, other embodiments are within the scope of the followingclaims.

1. A compound having the formula:

wherein: one of R¹ and R² is hydrogen and the other is a C₆-C₃₀ linearalkyl; and X is selected from the group consisting of:

wherein: R⁴ and R⁵ are independently selected from the group consistingof hydrogen; linear, branched, or cyclic alkyl; linear, branched, orcyclic alkenyl; aryl; and arylalkyl.
 2. A compound having the formula:

wherein: Y is selected from the group consisting of:

wherein: one of A or B is hydrogen and the other is selected from thegroup consisting of carboxyl, carboxylate salt, and ester; and m and nare independently integers from 0 to 20, wherein the sum of m+n is inthe range from 8 to
 21. 3. A compound having the formula:

wherein: Z is selected from the group consisting of:

wherein: one of A or B is hydrogen and the other is selected from thegroup consisting of carboxyl, carboxylate salt, and ester; and m and nare independently integers from 0 to 20, wherein the sum of m+n is inthe range from 8 to
 21. 4. A compound, or salt thereof, having theformula:

wherein: R⁶ is selected from hydrogen or a C₁-C₁₀ linear or branchedalkyl; and W is selected from the group consisting of:


5. A compound having the formula:

wherein: R⁶ is selected from hydrogen or a C₁-C₁₀ linear or branchedalkyl; and V is selected from the group consisting of:


6. The compound of any one of claim 1 or 3, wherein R⁴ and R⁵ are notboth hydrogen.
 7. A method for preparing a compound of claim 1, themethod comprising: a) providing a compound of the formula:

wherein: R³ is a C₆-C₃₀ linear alkyl; b) providing glycerol or acompound of the formula:

wherein: R⁴ and R⁵ are independently selected from the group consistingof hydrogen; linear, branched, or cyclic alkyl; linear, branched, orcyclic alkenyl; aryl; and arylalkyl; and c) effecting the reactionbetween the compounds of a) and b) in the presence of an acid or basecatalyst.
 8. The method of claim 7, wherein the method furthercomprises: d) deprotecting the ketal or acetal group.
 9. The method ofclaim 7, wherein R³ is a C₆-C₁₄ linear alkyl.
 10. A method for preparinga compound of any one of claims 2-4, wherein the method comprises: a)providing a glycerol or a compound of the formula:

wherein: R⁴ and R⁵ are independently selected from the group consistingof hydrogen; linear, branched, or cyclic alkyl; linear, branched, orcyclic alkenyl; aryl; and arylalkyl; b) providing a compound selectedfrom the group consisting of: an epoxidized triglyceride, and anepoxidized unsaturated fatty acid ester, wherein the fatty acid fragmenthas from 8 to 24 carbon atoms, and the alcohol fragment is a fragment ofa C₁-C₁₂ linear or branched monohydric alcohol; c) effecting a reactionbetween the compounds of a) and b) in the presence of an acid or basecatalyst; and d) deprotecting the ketal or acetal group.
 11. The methodof claim 10, wherein the method further comprises: e) converting thecarboxyl ester group to a free carboxyl group, a carboxylic salt, or anamide.
 12. A method for preparing a compound of claim 5, the methodcomprising: a) providing a glycerol or a compound of the formula:

wherein: R⁴ and R⁵ are independently selected from the group consistingof hydrogen; linear, branched, or cyclic alkyl; linear, branched, orcyclic alkenyl; aryl; and arylalkyl; b) providing a compound selectedfrom the group consisting of: an epoxidized triglyceride, and anepoxidized unsaturated fatty acid ester, wherein the fatty acid fragmenthas from 8 to 24 carbon atoms, and the alcohol fragment is a fragment ofa C₁-C₁₂ linear or branched monohydric alcohol; and c) effecting areaction between the compounds of a) and b) in the presence of an acidor base catalyst.
 13. The method of claim 12, wherein the method furthercomprises: d) converting the carboxyl ester group to a free carboxylgroup, a carboxylic salt, or an amide.
 14. The compound of claim 1,wherein R₁ is hydrogen.
 15. The compound of claim 1, wherein R₂ ishydrogen.
 16. The method of claim 7, wherein the glycerol or compound ofthe formula

is provided in a molar excess of 2 to 20 times molar excess relative tothe compound of the formula


17. The method of claim 8, wherein the deprotecting is carried out usingwater or a linear or branched primary or secondary alkanol having from 1to 6 carbon atoms.
 18. The method of claim 17, wherein the deprotectingis carried out in the presence of an acid catalyst under conditions thatdo not cause an elimination reaction.
 19. A compound having the formula:

wherein R₁ is a C₆-C₃₀ linear alkyl group and R₂ is an alkyl groupcomprising an ester or carboxyl functionality; and X is selected fromthe group consisting of

wherein R₄ and R₅ are independently selected from the group consistingof hydrogen, linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl,branched alkenyl, cyclic alkenyl, aryl, and alkaryl groups.
 20. Thecompound of claim 19, wherein R₄ and R₅ are not both hydrogen.
 21. Acomposition comprising a first compound and a second compound, the firstcompound having the formula

and the second compound having the formula

wherein, for both the first compound and the second compound, R₁comprises a C₆-C₃₀ linear alkyl group and R₂ comprises an alkyl groupcomprising an ester or carboxyl functionality; and X is selected fromthe group consisting of

wherein R₄ and R₅ are independently selected from the group consistingof hydrogen, linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl,branched alkenyl, cyclic alkenyl, aryl, and alkaryl groups.
 22. Thecomposition of claim 21, wherein R₄ and R₅ are not both hydrogen.
 23. Amethod for preparing the compound of claim 19, or the composition ofclaim 21, the method comprising: (a) providing an epoxide compound ofthe formula

wherein R₁ comprises a C₆-C₃₀ linear alkyl group and R₂ comprises analkyl group comprising an ester or carboxyl functionality; (b) providingglycerol or a protected glycerol compound of the formula

wherein R₄ and R₅ are independently selected from the group consistingof hydrogen, linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl,branched alkenyl, cyclic alkenyl, aryl, and alkaryl groups; and (c)reacting the compounds of a) and b) in the presence of an acid or basecatalyst.
 24. The method of claim 23, wherein the epoxide compoundcomprises an epoxidized monounsaturated fatty acid ester, an epoxidizeddiunsaturated fatty acid ester, an epoxidized triglyceride, of a mixturethereof.
 25. The method of claim 23, wherein the epoxide compoundcomprises epoxidized vegetable oil comprising soybean oil, linseed oil,canola oil, safflower oil, sunflower oil, corn oil, castor oil, or ablend thereof.
 26. The method of claim 23, wherein the epoxide compoundcomprises a mixture of methyl esters of fatty acids derived bytransesterification and epoxidation of a vegetable oil.
 27. The methodof claim 23, further comprising d) deprotecting the protected glycerol.